RU2278877C2 - Thermoplastic halogenated elastomer compositions - Google Patents

Abstract

FIELD: polymer materials.

SUBSTANCE: invention relates to elevated-viscosity thermoplastic halogenated elastomer compositions and to a process for preparing the same. Composition according to invention contains thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound having the respective structure R₁R₂ R₃N or R₁R₂R₃P wherein R₁ is H or C-₁-C₆-alkyl, R₂ is C₁-C₃₀-alkyl and R₃ is C₄-C₃₀-alkyl and further wherein R₃ represents alkyl higher than R-₁. A process for preparing elevated-viscosity thermoplastic composition consists in mixing thermoplastic polymer, at least one isoolefin copolymer comprising unit derived from halomethylstyrene, and at least one hindered amine or phosphine compound to obtain thermoplastic elastomer compositions, including dynamically cured ones, containing more finely dispersed elastomer.

EFFECT: improved mechanical properties.

4 cl, 10 tbl

Description

FIELD OF THE INVENTION

The present invention relates to halogenated elastomers having increased viscosity, and to a thermoplastic elastomer composition comprising such elastomers. These thermoplastic elastomeric compositions are mixtures of an isoolefin copolymer comprising at least a halomethylstyrene derivatized unit and at least one amine or phosphine.

BACKGROUND OF THE INVENTION

A thermoplastic elastomer is usually defined as a polymer or a mixture of polymers that can be processed and recycled in the same way as conventional thermoplastic materials, and which nevertheless has properties and performance characteristics similar to those that vulcanized rubber has at operating temperatures.

Mixtures or alloys of plastic and elastomeric rubber are becoming increasingly important in the production of high performance thermoplastic elastomers, especially as substitutes for thermoset rubber in various applications.

Polymer mixtures that have a combination of both thermoplastic and elastic properties are usually prepared by combining a thermoplastic polymer with an elastomeric composition so that the elastomer is homogeneously and uniformly dispersed as a phase of discrete particles in the continuous phase of the thermoplastic material. An early work on vulcanized compositions was discovered in U.S. Pat. No. 3,037,954, which describes static vulcanization as well as dynamic vulcanization technology, in which a vulcanizable elastomer is dispersed in a resinous thermoplastic polymer and the elastomer is vulcanized while continuously mixing and shearing the polymer mixture. The resulting composition is a microgel dispersion of a vulcanized elastomer, such as butyl rubber, chlorinated butyl rubber, polybutadiene and polyisoprene, in a non-crosslinked matrix of a thermoplastic polymer such as polypropylene.

Depending on the end use, such thermoplastic elastomeric (TPE) compositions may include one or a mixture of thermoplastic materials such as propylene homopolymers and propylene copolymers and the like. thermoplastic materials used in combination with one or a mixture of vulcanized or unvulcanized elastomers, such as ethylene-propylene rubber, TEPD (triple ethylene-propylene with diene units) rubber, diolefin rubber, butyl rubber or similar elastomers. TPE compositions can also be prepared when the thermoplastic material used is a structural resin having good high temperature properties, such as polyamide or polyester, used in combination with a vulcanized or unvulcanized elastomer. Examples of such TPE compositions and methods for processing such compositions, including methods of dynamic vulcanization, can be found in US 4130534, 4130535, 4594390, 5021500, 5177147 and 5290886, as well as in WO 92/02582.

Particularly preferred elastomeric polymers that can be used to prepare TPE compositions are halogenated random isoolefin copolymers comprising at least halomethyl styrene derivatives. Halogenated elastomeric copolymers of this type (designated as BIMS polymers; brominated isobutylene-p-methylstyrene copolymers) and a method for their preparation are described in US 5162445. Vulcanizable TPE compositions comprising these copolymers are described, in addition to other literature, in US 5013793 and 5051477.

TPE compositions are usually prepared by melt mixing or melt processing of thermoplastic and elastomeric components at temperatures exceeding 150 ° C and under conditions of mixing with a high shear rate (shear rate above 100 1 / s or s ^-1 ) in order to prepare a fine dispersion of one a polymer system in a matrix of another polymer system. The finer the dispersion, the better the mechanical properties of the TPE product.

Due to the activation of the outflow and the liquefaction characteristics under the influence of shear forces inherent in such SIMS polymers, the values of viscosity reduction of these polymers at elevated temperatures and shear rates that are natural during mixing turn out to be much more pronounced than the decrease in viscosity of the thermoplastic component with which SIMS is mixed polymer. However, the difference in minimizing the viscosity of SIMS and thermoplastic components during mixing and / or processing is essential to achieve uniform mixing and fine morphology of the mixture, which is crucial for the good mechanical properties of the mixture.

Summary of the invention

The invention provides a composition, preferably a thermoplastic composition, comprising a halogenated elastomer and a viscosity increasing additive such as a difficult amine or phosphine. In one embodiment, the halogenated elastomer is a C ₄ to C ₇ isomonoolefin copolymer comprising halomethyl styrene derivatized units. This copolymer is mixed with at least one hindered amine or phosphine compound having the corresponding structure (R ₁ R ₂ R ₃ ) N or (R ₁ R ₂ R ₃ ) P, where R ₁ is H or C ₁ to C ₆ alkyl , R ₂ is C ₁ to C ₃₀ alkyl, and R ₃ is C ₄ to C ₃₀ alkyl, and furthermore, where R ₃ is higher alkyl than R ₁ , said mixture being carried out at a temperature that exceeds the temperature melting said hindered amine or phosphine compound. In a preferred embodiment, the mixing is carried out so as to create a homogeneous mixture.

The invention further provides a method for increasing the viscosity of a C ₄ to C ₇ isomonoolefin copolymer comprising mixing the copolymer with a hindered amine or phosphine compound.

The invention proposes a new technique aimed at increasing the viscosity of SIMS copolymers so that their viscosity during high shear thermal mixing is more closely approximated to the viscosity of thermoplastic materials with which they are mixed, thereby simplifying more uniform mixing and formation of more fine dispersion of one polymer system in the matrix of another polymer system.

DETAILED DESCRIPTION OF THE INVENTION

In the sense in which it is used in the present description, the term "dynamic vulcanization" means the process of vulcanization or curing of rubber contained in a thermoplastic elastomeric composition in which rubber is vulcanized at high shear conditions at a temperature that exceeds the melting temperature of the thermoplastic component. Thus, rubber is simultaneously structured and dispersed in the form of fine particles in a thermoplastic matrix, although, as noted above, other structures are also possible.

In the sense in which it is used in the present description, the term “vulcanized” means that the rubber component to be vulcanized is vulcanized to a state in which the elastomeric properties of the structured rubber are similar to those of a rubber in its usual vulcanized state, not to mention About thermoplastic elastomeric composition. The degree of vulcanization can be expressed by the values of the gel content or, conversely, the content of extractable components. In another embodiment, the degree of vulcanization can be expressed in terms of the density of the crosslinking. All these characteristics in the art are well known and are presented, for example, in US 5100947 and 5157081.

As used herein, the term “composition” encompasses mixtures of a halogenation product of C ₄ to C ₇ isomonoolefin static copolymers, such as isobutylene, and an alkyl styrene comonomer, with an additive to influence viscosity, such as amine or phosphine . The composition may also include other components.

In the present description of the link to the “groups” of the Periodic Table of Elements, a new numbering scheme for the groups of the Periodic Table of Elements is used, which is presented in Hawley's Condensed Chemical Dictionary 852 (13th ed. 1997).

As used herein, the term “elastomer” refers to any polymer or polymer composition meeting the definition of ASTM D 1566. The terms “elastomer” and “rubber” as used herein can be used interchangeably.

An isoolefin copolymer comprising a halomethyl styrene derivatized unit

The compositions of the present invention include at least one halogenated elastomer. In one embodiment of the invention, the halogenated elastomer is a random copolymer comprising at least units derived from C ₄ to C ₇ isoolefin, such as units derived from isobutylene and units derived from halomethyl styrene. The halomethylstyrene unit may be an ortho-, meta-, or para-alkyl-substituted styrene unit. In one embodiment, the halomethyl styrene derivatized unit is p-halomethyl styrene containing at least 80%, more preferably at least 90 wt.%, Para-isomer. As a “halogen group”, any halogen atom may be present, preferably a chlorine or bromine atom. The halogenated elastomer may also include functionalized copolymers in which at least some of the alkyl substituent groups present on the styrene monomer units contain a benzyl halogen atom or some other functional group, further described below. These copolymers are referred to herein as “isoolefin copolymers comprising a unit derived from halomethylstyrene”, or simply “isoolefin copolymers”.

The isoolefin copolymer may also include units derived from other monomers. The isoolefin of the copolymer may be a C ₄ to C ₁₂ compound, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1 butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene and 4-methyl-1-pentene. Such a copolymer may also further include units derived from a multiolefin. A multiolefin is a C ₄ to C ₁₄ polyunsaturated olefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene, as well as other monomers such as described in EP 0279456 and US 5506316 and 5162425. Suitable units derived from styrene monomers that may be present in the copolymer include styrene, methyl styrene, chlorostyrene, methoxystyrene, indene, indene derivatives and combinations thereof.

In another embodiment, the copolymers are random elastomeric copolymers of a unit derived from ethylene or a unit derived from a C ₃ to C ₆ α-olefin and a unit derived from halomethyl styrene, preferably p-halomethyl styrene, containing at least 80% , more preferably at least 90 wt.%, of the para-isomer, and also include functionalized copolymers in which at least some alkyl substituent groups located in styrene monomer units contain benzylic halogen or some other functional group.

Preferred isoolefin copolymers can be characterized as copolymers comprising the following monomer units, statistically placed along the polymer chain:

in which each of R and R ¹ independently represents a hydrogen atom, lower alkyl, preferably C ₁ to C ₇ alkyl, or primary or secondary alkyl halide, and X represents a functional group such as a halogen atom. Suitable halogen atoms are chlorine, bromine or a combination thereof. In a preferred embodiment, each of R and R ¹ represents a hydrogen atom. The groups —CRR ₁ H and —CRR ₁ X can be substituents on the styrene ring in either the ortho, or meta, or para position, preferably in the para position. Up to 60 mol% of p-substituted styrene units included in the copolymer structure may have the above functionalized structure (2) in one embodiment and from 0.1 to 5 mol% in another embodiment. Nevertheless, in yet another embodiment, the content of the functionalized structure (2) is from 0.4 to 1 mol%.

Functional group X may be a halogen atom or some other functional group that can be introduced by nucleophilic substitution of a benzyl halogen atom by other groups, such as carboxylic acid residues, carboxylic acid salts, carboxylic acid esters, amides and imides, hydroxyl, alkoxide, phenoxide , thiolate, thioether, xanthate, cyanide, cyanate, amino group and mixtures thereof. These functionalized isomonoolefin copolymers, the method for their preparation, methods of functionalization and vulcanization are more specifically described in US 5162445.

The most widely used of these functionalized materials are elastomeric random copolymers of isobutylene and p-methyl styrene, comprising from 0.5 to 20 mol% of p-methyl styrene units, in which up to 60 mol% of methyl substituent groups on the benzyl ring contain a bromine atom or chlorine, preferably a bromine atom (p-bromomethylstyrene), as well as their variants functionalized by acid or ester residues, in which the halogen atom is substituted by a residue of maleic anhydride or acrylic or methacrylic acid. These copolymers are called “halogenated isobutylene / p-methyl styrene copolymers” or “brominated isobutylene / p-methyl styrene copolymers”, they are technically available as EXXPRO ™ elastomers (ExxonMobil Chemical Company, Houston, TX). It is obvious that the use of the terms “halogenated” or “brominated” is not limited to the method of halogenation of a copolymer, they simply serve to describe a copolymer that includes units derived from isobutylene, units derived from p-methylstyrene, and units derived from p-halomethylstyrene .

In a preferred embodiment, these functionalized polymers have a substantially homogeneous compositional distribution, whereby the content of p-alkylstyrene units in at least 95% by weight of the polymer is in the 10% range relative to the average content of p-alkylstyrene units in the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw / Mn) of less than 5, more preferably less than 2.5, a preferred average viscosity molecular weight in the range of 200,000 to 2,000,000, and a preferred number average molecular weight in the range of 25,000 to 750,000, as this is determined by gel permeation chromatography.

Such copolymers can be prepared by suspension polymerization of a monomer mixture using a Lewis acid as a catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a free radical polymerization initiator, such as heat and / or light, and / or a chemical initiator, and optional subsequent electrophilic substitution of the bromine atom with another functional derivatized unit.

Preferred halogenated isobutylene / p-methylstyrene copolymers are brominated polymers, which typically contain from 0.1 to 5 wt.% Bromomethyl groups. Nevertheless, in yet another embodiment, the number of bromomethyl groups is from 0.2 to 2.5 wt.%. To put it differently, preferred copolymers contain from 0.05 to 2.5 mol% of bromine atoms based on the weight of the polymer, more preferably from 0.1 to 1.25 mol% of bromine atoms, and are substantially free of ring halogen atoms or halogen atoms in the main polymer chain. In one embodiment, the copolymer is a copolymer of units derived from C ₄ to C ₇ isomonoolefin, units derived from p-methylstyrene, and units derived from p-halomethyl styrene, wherein the p-halomethyl styrene units are in the amount of from 0.4 to 1 molar%, calculated on the copolymer. In another embodiment, this p-halomethylstyrene is p-bromomethylstyrene. Mooney viscosity (1 + 8, 125 ° C, ASTM D1646 standard, modified method) is from 30 to 60 units. measurements.

Amine / phosphine component

Increasing the viscosity of the SIMS copolymers is achieved by mixing the SIMS copolymer with the corresponding hindered amine or phosphine compounds (or “viscosity improvers”) under shear and at temperatures that exceed the melting temperature of the amine or phosphine for a period of time sufficient to to allow the amine or phosphine to be uniformly dispersed in the BIMS material, typically from 1 to 10 minutes, and at preferred temperatures in the range of 100 to 180 ° C.

Suitable preferred viscosity improvers that can be used include those that correspond to the formula (R ₁ R ₂ R ₃ ) Q, in which Q is an element of group 15, preferably a nitrogen or phosphorus atom, and in which R ₃ is alkyl with C ₁₀ at C ₂₀ , a R ₁ and R ₂ that are the same or different, are lower alkyls, more preferably C ₁ to C ₆ alkyls. Of the hindered amine / phosphine compounds that can be used, preferred include those tertiary amines that correspond to the above formula (R ₁ R ₂ R ₃ ) N. Particularly preferred amines are decyldimethylamine, hexadecyldimethylamine, hydrogenated tall oil alkyl dimethyl amines, dihydrogenated tall oil alkyl methyl amines and the like. connections.

Preferred hindered phosphine compounds of the formula (R ₁ R ₂ R ₃ ) P are also those in which R ₃ is C ₁₀ to C ₂₀ alkyl, and R ₁ and R ₂ that are the same or different, are lower alkyls, more preferably alkyls C ₁ to C ₆ . These phosphines are analogues of the above amines.

The amount of amine or phosphine introduced into the BIMS copolymer should be sufficient to increase the viscosity of the composition (increase at a given shear rate and temperature). The resulting composition can be called in different ways: as an “amino or phosphino / copolymer” composition or as a “viscosity improver / copolymer” composition, or as an “amine or phosphine / BIMS" composition. In one embodiment, the viscosity value of the composition "viscosity improver / BIMS" at 220 ° C and a shear rate of 100 1 / s exceeds 1300, in another embodiment, this value at 220 ° C and a shear rate of 100 1 / s is from 1300 to 6000 Pa · S and at 220 ° C and a shear rate of 100 1 / s - from 1400 to 5000 Pa · s in another embodiment. In another embodiment, the viscosity value of the composition of the additive for increasing the viscosity / BIMS at 220 ° C and a shear rate of 1000 1 / s exceeds 200, in another embodiment, this value at 220 ° C and a shear rate of 1000 1 / s is from 200 to 600 Pa · s and at 220 ° C and a shear rate of 1000 1 / s - from 220 to 550 Pa · s in another embodiment. Typically, 0.05 to 2 molar equivalents, more preferably 0.1 to 1 molar equivalents of amine or phosphine per HIMS halogen are sufficient.

The viscosity improver / SIMS, amine / SIMS composition in one embodiment of the present invention is prepared essentially in the absence of solvent. More specifically, the amine and BIMS components are mixed according to methods known to those skilled in the art without the addition of an organic solvent. In the composition or during mixing of the components, solvents, mainly organic solvents, are essentially absent. By the term “substantially absent” is meant that less than 5 wt.% Of solvent is contained by weight of the total composition available and less than 2 wt.% In another embodiment.

Modified BIMS polymers of the present invention should be distinguished from the ionomers described in US 5162445 or WO 94/10214. The preparation of such materials according to these references includes nucleophilic substitution reactions carried out in an organic solvent in which the benzyl halogen atom contained in the BIMS polymer is replaced, thereby converting the polymer into an ionomer with an ionic amine or phosphine functional group. The materials obtained in accordance with the present invention are believed to be ionically coupled polymer chains without any substitution of the halogen atom in the polymer chains. Thanks to this association of ions, a modified polymer is created having a higher viscosity compared to the viscosity of the original SIMS polymer.

Thermoplastic polymers

The high viscosity isoolefin copolymer according to the invention can be used for mixing with thermoplastics. Thermoplastic polymers suitable for use in carrying out the present invention include amorphous, partially crystalline or substantially completely crystalline polymers selected from polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, polyacetals, acrylonitrile butadiene-styrene copolymer resins, polyphenylene oxides, copolymers of ethylene / carbon monoxide, polyphenylene sulfides, polystyrene, styrene-acrylonitrile copolymer resins, resins from styrene copolymers and / maleic anhydride, aromatic polyketones and mixtures thereof. These and other thermoplastics are described, for example, in US 6013727.

Polyolefins suitable for use in the compositions of the invention include thermoplastic, at least partially crystalline polyolefin homopolymers and copolymers, including polymers prepared using Ziegler-Natta type catalysts or single site catalysts such as metallocene catalysts. It is advisable to obtain them from monoolefin monomers, each of which contains from 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, copolymers including the units of these monomers, etc., with the preferred monomer is propylene. Used in the description and claims, the term "polypropylene" covers propylene homopolymers, as well as propylene reactor copolymers, which may include from 1 to 20 wt.% Units of ethylene or alpha-olefin comonomer containing from 4 to 16 carbon atoms, and mixtures thereof. Polypropylene can be highly crystalline isotactic or syndiotactic polypropylene, typically having a narrow glass transition temperature (Tc) range. When carrying out the invention, technically available polyolefins can be used.

The term "polypropylene" covers propylene homopolymers, as well as a polypropylene reactor copolymer, which may include from 1 to 20 wt.% Of ethylene derivatized units or units derived from another α-olefin comonomer containing from 4 to 6 carbon atoms. Polypropylene can be highly crystalline isotactic or syndiotactic polypropylene. The reactor copolymer can be either random or block copolymer. Other suitable thermoplastic polyolefin resins include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ethylene copolymer resins, plastomer copolymers of ethylene and 1-alkene, polybutene and mixtures thereof.

Acceptable thermoplastic polyamides (nylons) include crystalline or resinous high molecular weight solid polymers, including copolymers and ternary copolymers containing repeating amide units in the polymer chain. Polyamides can be prepared by polymerization of one or more epsilon-lactams, such as caprolactam, pyrrolidinone, laurillactam and aminoundecane lactam, or amino acids, or by polycondensation of dibasic acids and diamines. Suitable nylons as fiber-forming and molding varieties. Examples of such polyamides are polycaprolactam (nylon-6), polylaurillactam (nylon-12), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene azelamide (nylon-6,9), polyhexamethylene sebacamide (nylon-6,10), polyhexamethylene isophthalamide (nylon 6 , IF) and the polycondensation product of 11-aminoundecanoic acid (nylon-11). When carrying out the present invention, technically available thermoplastic polyamides can also be effectively used, linear crystalline polyamides having a softening or melting point in the range of 160 to 230 ° C. are preferred.

Suitable thermoplastic polyesters that may be used include polymeric reaction products of one or a mixture of aliphatic or aromatic polycarboxylic acids, esters or anhydrides, and one or a mixture of diols. Examples of suitable polyesters include poly (trans-1,4-cyclohexylene), poly (alkane (C ₃ to C ₆ ) biscarboxylates) such as poly (trans-1,4-cyclohexylene succinate) and poly (trans-1,4 β-cyclohexylene adipate); poly (cisili-trans-1,4-cyclohexanedimethylene) alkanedicarboxylates such as poly (cis-1,4-cyclohexanedimethylene) oxalate and poly (cis-1,4-cyclohexanedimethylene) succinate; poly (alkylene (C ₂ to C ₄ ) terephthalates) such as polyethylene terephthalate and polytetramethylene terephthalate; poly (alkylene (C ₂ to C ₄ ) isophthalates) such as polyethylene isophthalate and polytetramethylene isophthalate, and the like. materials. A preferred polyester is derivatized from aromatic dicarboxylic acids, such as naphthalenedicarboxylic and ophthalmic acids, and C ₂ to C ₄ diols, such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters are usually characterized by a melting point in the range from 160 to 260 ° C.

Polyphenylene ether (PFE) thermoplastic structural resins that can be used in accordance with the present invention are well known technically available materials obtained by the oxidative dehydrocondensation polymerization of alkyl substituted phenols. Usually they are linear polymers, the glass transition temperature of which is in the range from 190 to 235 ° C. Examples of preferred PFE polymers include poly-2,6-dialkyl-1,4-phenylene ethers, such as poly-2,6-dimethyl-1,4-phenylene ether, poly-2-methyl-6-ethyl-1,4 -phenylene ether, poly-2,6-dipropyl-1,4-phenylene ether and poly-2-ethyl-6-propyl-1,4-phenylene ether. These polymers, the method for their preparation and mixtures with polystyrene are additionally described in US 3383435.

Other thermoplastic resins that can be used include polycarbonate analogues of the polyesters described above, such as segmented ether and phthalate copolymers; polycaprolactone polymers; styrene resins such as styrene copolymers with less than 50 mol% acrylonitrile (SAN) and resin copolymers of styrene, acrylonitrile and butadiene (ABS); sulfonic polymers such as polyphenyl sulfone and the like. structural resins that are known in the art.

Additives

The compositions of the invention may include plasticizers, vulcanizing groups and may also include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, oils for improving the technological properties of rubber, plasticizers, oils for filling rubber in the latex stage, lubricants, release agents, antistatic agents, waxes, blowing agents, pigments , flame retardants and other substances for improving technological properties, known in the technique of preparing rubber compounds. Such additives may comprise up to 50% by weight of the total composition. Excipients and diluents that can be used include conventional inorganic materials such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black, and the like. Oils for improving the technological properties of rubber are usually petroleum jelly, naphthenic or aromatic petroleum oils derived from petroleum fractions, but preferably petrolatum. Use oils of the type that is usual in combination with the particular rubber or rubbers contained in the composition, and the amount, calculated on the total rubber content, can be in the range from zero to 1-200 parts by weight. one hundred parts of rubber (frequent / 100). The composition of the composition may also contain plasticizers, such as trimellitate esters.

Moreover, various phenolic resins known in the art and literature can be used, as well as various phenol-formaldehyde resins, as presented in "The Chemistry of Phenol-Formaldehyde Resin Vulcanization of EPDM: Part I. Evidence for Methylene Crosslinks," by Martin Van Duin and Aniko Souphanthong, 68 Rubber Chemistry and Technology 717-727 (1995).

The vulcanizing agent of the present invention may include any number of components, such as a complex based on a metal or metal-containing ligand, accelerators, resins, or other components known in the art as affecting vulcanization of an elastomer. In its broadest embodiment, the curative is at least a metal oxide or complex with a ligand based on a metal of groups 2-14, where at least one ligand is capable of undergoing substitution in reaction with an inducing compound. In one embodiment, the at least one curing agent is a metal oxide, in particular such as. zinc oxide, hydrated lime, magnesium oxide, carbonates and hydroxides of alkali metals. Thus, in particular, conventional vulcanizing groups, which are typically used in the practice of the present invention, include the following metal-based vulcanizing substances: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO , and / or carboxylates of these metals. These metal oxides can be used in combination with the corresponding complex based on a metal carboxylate or with a carboxylate ligand and either with a sulfur compound or an alkyl peroxide compound [see also Formulation Design and Curing Characteristics of NBR Mixes for Seals, Rubber World 25-30 (1993)].

These metal oxides can be used in combination with another compound, such as a fatty acid, and the range of the curing agent in the present description is not limited to one metal oxide or complex with a metal-containing ligand. Examples of organic or fatty acids that can be used in carrying out the invention are stearic, oleic, lauric, palmitic, myristic acids and mixtures thereof, as well as hydrogenated oils from a number of palm, castor oils, fish oil and linseed oil. The use of these vulcanizing agents is discussed in Rubber Technology 20-58 (Maurice Mortin, ed .. Chapman & Hall 1995) and Rubber World Magazine's Blue Book 2001 109-137 (Don R. Smith, ed., Lippincott & Peto, Inc. 2001 ), as well as in US 5332787.

The amount of vulcanizing agent usually varies depending on the type of substance used and in particular on the target degree of vulcanization, as is well known in the art. So, for example, the amount of sulfur is usually from 1 to 5, and preferably from 2 to 3, parts by weight. per 100 parts by weight composition. The amount of peroxide curing agent is usually from 0.1 to 2.0 parts by weight, the amount of phenolic curing resin is usually from 2 to 10 parts by weight, and the amount of hindered amine is from 0.1 to 2 parts by weight, and all quantities are indicated in terms of 100 wt.chast. composition.

In one embodiment of the invention, the curing groups may be contained in an amount of from 0.5 to 20 parts / 100 of the composition and from 1 to 10 parts / 100 in another embodiment. In yet another embodiment, vulcanizing groups in the composition are essentially absent. By the term “substantially absent” is meant that traditional vulcanizing groups such as phenolic resins, sulfur, peroxides, metals and metal oxides and complexes with metal-containing ligands are not contained in the composition.

Processing

The BIMS component of a thermoplastic elastomer is usually contained as small, i.e. micrometric size, particles in a continuous plastic phase, although depending on the amount of rubber relative to the plastic material and the vulcanizing group or the degree of vulcanization of the rubber, joint continuous morphology or phase inversion is also possible. In the final vulcanized thermoplastic composition, it is advisable to at least partially structure the rubber, and in the preferred embodiment, it is structured in whole or in full. Partial or complete crosslinking can be achieved by adding a suitable vulcanizing rubber group to the thermoplastic polymer / rubber mixture and vulcanizing the rubber to the target degree under normal vulcanizing conditions. However, in a preferred embodiment, the rubber should be structured by dynamic vulcanization.

Dynamic vulcanization is carried out by mixing thermoplastic and elastomeric components at elevated temperatures in conventional mixing equipment, such as rollers, Banbury ™ mixers, Brabender ™ mixers, continuous rubber mixers, mixing syringes, etc. A unique characteristic of dynamically vulcanized compositions is that, despite the fact that the rubber component is partially or completely vulcanized, such compositions can be processed and recycled using conventional plastic materials processing techniques, such as extrusion, injection molding, blow molding and direct compression. Waste or waste can be disposed of and recycled.

Appropriate amounts, types of vulcanizing groups and vulcanization conditions that are necessary for the vulcanization of SIMS rubber are apparent to those skilled in the art. The rubber can be vulcanized using varying amounts of a vulcanizing group, with varying temperatures and with varying vulcanization times in order to achieve the desired optimum crosslinking. You can use any known vulcanizing group for rubber, if only it was acceptable in the conditions of vulcanization, taking into account the specifically used BIMS rubber and thermoplastic component. These vulcanizing groups include sulfur, sulfur donors, metal oxides, resin systems, peroxide-based groups, hydrosilylating vulcanizing groups, platinum or peroxide catalysts, and the like. both with accelerators and joint vulcanizing agents, and without them. Such vulcanizing groups are well known in the art and in the literature on vulcanization of elastomers.

Depending on the intended application, the amount of rubber contained in the composition may range from 10 to 90% by weight of the total polymer in the composition. For most applications, especially when the rubber component is vulcanized dynamically, the amount of this rubber component is usually less than 70 wt.%, More preferably less than 50 wt.%, And most preferably from 10 to 40 wt.%, Of the total polymer content in the composition .

The processing temperature of TPE compositions in the melt is usually in the range from a temperature above the melting point of the highest melting polymer contained in the TPE composition to 300 ° C. Preferred processing temperatures are usually in the range from 140 to 260 ° C., from 150 to 240 ° C. in another embodiment, and yet from 170 to 220 ° C. in yet another embodiment.

A hindered amine or phosphine compound can be combined with the SIMS rubber component at any mixing stage, i.e. when SIMS and a thermoplastic polymer are initially mixed, or while vulcanizing groups or other additives are mixed in the preparation of dynamically vulcanized compositions. However, in a preferred embodiment, the hindered amine or phosphine material is first compounded with a SIMS polymer at temperatures up to 300 ° C. to produce a modified SIMS polymer with increased viscosity, and then this modified polymer is mixed with a thermoplastic resin and all other additives contained in the TPE composition.

The thermoplastic composition of the invention is formed by mixing in any order an amine or phosphine, an isoolefin copolymer and a thermoplastic material. In one embodiment, the copolymer is first mixed with an amine or phosphine to form an amine or phosphine / copolymer composition, followed by mixing with a thermoplastic material. In another embodiment, these three components are mixed simultaneously. Moreover, in one embodiment of the present invention, such a thermoplastic composition is prepared in the absence of a solvent. More specifically, the amine and BIMS components are mixed according to a method known to those skilled in the art without the addition of an organic solvent. Further, the thus prepared amine or phosphine / copolymer composition can be mixed in the absence of a solvent with a thermoplastic material. Solvents, mainly organic solvents such as hexane, methylene chloride and other solvents, which are known as solvent polyolefins, nylons and halogenated elastomers, are essentially absent in the composition or during mixing of the components. By the term “substantially absent” is meant that the solvent content is less than 5 wt.%, Based on the weight of the entire composition available.

The thermoplastic compositions of the invention may include from 10 to 90 wt.% Thermoplastic material and from 90 to 10 wt.% Isoolefin copolymer. In another embodiment, the thermoplastic compositions of the invention may include from 20 to 80 wt.% Thermoplastic material and from 80 to 20 wt.% Isoolefin copolymer. In yet another embodiment, the thermoplastic compositions of the invention comprise from 40 to 60 wt.% Thermoplastic material and from 60 to 40 wt.% Isoolefin copolymer. Vulcanized thermoplastic compositions have a tensile strength of more than 1000 psi in one embodiment and more than 2000 psi in another embodiment (ASTM D 1708, as described below). Such vulcanized thermoplastic compositions have a rupture at break value of more than 200% in one embodiment and more than 300% in another embodiment (ASTM D 1708, as described below).

EXAMPLES

The invention is illustrated by the following examples. The materials used in these examples are presented in table 1.

Example 1

This example illustrates the decrease in viscosity of brominated isobutylene / p-methylstyrene copolymer (indicated in table 1 as BIMS 1, 2 and 3). Samples of each rubber were subjected to shear at shear rates from 50 to 5000 s ^-1 using a capillary plastometer at a temperature of 220 ° C. The viscosity data was subsequently corrected for inlet pressure and non-Newtonian flow profile. For comparison, only viscosity values are presented at 100, 500, 1000 and 1500 s ^-1 . Table 2 shows the viscosity drop for each of these rubbers as a function of shear rate increase.

Example 2

All tertiary amines, DM16D, DMHTD and M2HT, were mixed in BIMS 2 using a Brabender ™ mixer, which was operated at 150 ° C and at 60 rpm. Amine was added in amounts that were molar equivalent to the content of bromine atoms in BIMS. As the data in Table 3 show, the addition of DM16D was able to increase the viscosity of the SIMS at 220 ° C at all shear rates.

The presence of the tertiary amine DM16D in the BIMS did not lead to any thermal degradation of the BIMS, as shown by the data in Table 4. The viscosity values of the BIMS after adding DM16D at each temperature remained relatively unchanged during cyclic exposure to heat in the range from 100 to 250 ° C.

The increase in viscosity as a result of the modification of BIMS with a tertiary amine depends on the structure of the amine. If we compare the data in table 5 with the data in table 3, then hexadecyldimethylamine DM16D provides a greater increase in viscosity compared to the increase with DMHTD, which is dimethyl, but with predominantly C ₁₈ group R ₃ in contrast to C ₁₆ group R ₃ in DM16D. When M2HT was used, which is a dihydrogenated tall oil alkylmethylamine and possesses both R ₂ and R ₃ groups as predominantly C ₁₈ alkyl groups (see data in Table 6), the increase in viscosity became less significant compared to that achieved by adding DM 16 D.

Example 3

A mixture comprising 60 wt.% Polypropylene with CPP (melt spreading rate) 1.5 (ExxonMobil, PP 4292) and 40 wt.% BIMS 2, modified 0.5 mol. Equiv. DM16D was prepared by mixing the components using a Brabender ™ mixer at 80 rpm and 220 ° C for a 5-minute period.

A control mixture was prepared, which was identical in all other respects, except that BIMS 2 was not modified with an amine (control mixture). The structural characteristics of the resulting mixture were studied by AFM (atomic force microscopy), followed by image processing to determine the size of the dispersed particles in units of number average equivalent diameter. In order to prevent relaxation of the samples, all samples were analyzed for 8 h after trimming the end in the frozen state. In the process of trimming the end face in the frozen state, these samples were cooled to -150 ° C and cut with diamond knives in a Reichert cryogenic microtome. Then, to warm to room temperature without condensation, they were stored in an oven in a stream of dry nitrogen gas. Finally, for AFM analysis, specimens with trimmed ends were placed in a miniature steel vise. AFM measurements were carried out in air under a NanoScope Dimension 3000 scanning electron microscope (digital measuring instrument) using a rectangular Si console. AFM phase images of all samples were converted in TIFF format and processed using a PHOTOSHOP ™ device (Adobe Systems, Inc.). For measuring image research, a set of image processing tools (Reindeer Games, Inc.) was used. The results of the measurement studies of the images were recorded in a text file for subsequent data processing using the EXCEL ™ program. The data obtained are presented in table 7. These results demonstrate an almost 30% decrease in the particle size of the dispersed SIMS rubber compared to their size in the control sample.

In the following examples, additional thermoplastic mixtures or compositions of ionically bonded alloys (ISS) containing varying amounts of tertiary amine were prepared, and their mechanical properties were evaluated in comparison with the properties of control samples that did not contain tertiary amine additives. The thermoplastic polymer used in these mixtures was PP4722 polypropylene (PP), CPP 2.8 polypropylene, available from ExxonMobil Chemical Co.

Example 4

The tertiary amine, when it was added to the mixture of thermoplastic material with an elastomer, was diluted with liquid paraffin. The PP / BIMS mixtures were prepared by mixing them in a Brabender mixer at a temperature of 190 ° C and a rotor speed of 60 rpm. PP granules were first melted in the presence of a suitable stabilizer, such as Irganox 1076. Subsequently, an elastomer was added, followed by Armeen DM16D, an oil-diluted product. Finally, metal oxide, for example MgO, was also added to this mixture to act as an acid binding agent. Table 8 presents several ISS compositions with a ratio of thermoplastic material / elastomer in a 40/60 mixture (quantities are expressed in mass parts). In the case of the composition according to the invention (b), an exact stoichiometric pair was selected according to the content of bromine and amino groups, while in the compositions of the invention (a) and (c) there were respectively more and less amino groups than the amount of bromine.

Each SSS composition of Table 8 was subjected to direct compression molding at 190 ° C. for 15 minutes to obtain plates of a thickness of about 0.08 inches. Using these molded plates (stored at room temperature for 48 hours prior to testing), tests were performed to determine the tensile stress / strain characteristics. For this purpose, samples in the form of micro-dumbbells were used (ASTM D 1708 standard) (test temperature: 25 ° C; Instron machine slider speed: 2 inches / min). As the data in table 8 show, the introduction of ion association in a PP / BIMS / oil mixture [examples of compositions of the invention from (a) to (c) containing 10 parts / 100 oil] significantly increased the strain at break, the maximum stress near the moment tensile strength and tensile strength (determined by the area under the stress-strain curve) in comparison with the characteristics of the material of the control example.

Example 5

Data for other ISS compositions with a ratio of thermoplastic material / elastomer in a mixture of 30/70 are presented in table 9 (quantities are expressed in mass parts). In the cases of compositions (g) and (e) of the invention, respectively, with 10 and 20 ppm 100 oils, the exact stoichiometric pair was selected with respect to the bromine and amino groups. Here again, it can be noted that the introduction of ion associations in the PP / BIMS / oil mixture (10 or 20 ppm / 100 oil) significantly increased the strain at break, the maximum stress near the moment of break and the tensile strength in comparison with the characteristics of control materials .

Table 10 presents the ISS composition with a ratio of thermoplastic material / elastomer in a mixture of 30/70, prepared using BIMS with a higher Mooney viscosity. The oil content was also varied in this series. In the cases of compositions (e), (g) and (h) according to the invention, the exact stoichiometric pair was selected with respect to the bromine and amino groups. The results show that the introduction of the ion association in the PP / BIMS / oil mixture (10, 20 or 30/100 oils) increased the maximum stress near the moment of rupture and the tensile strength in comparison with the same characteristics of the materials in the control examples. At a higher oil content, the strain at break at the mixture without ion associations turned out to be higher than that of the corresponding mixture with ion associations, possibly due to the higher molecular weight of BIMS 2.

Although the present invention has been described and illustrated with reference to specific embodiments, it will be apparent to those of ordinary skill in the art that the essence of the invention will lead to many different variations, which are not illustrated in the present description. For these reasons, in order to determine the actual scope of the present invention, it is only necessary to refer to the attached claims.

All priority documents mentioned in the present description are included in it in full in accordance with all jurisdictions that allow such inclusion. Moreover, in accordance with all jurisdictions that allow such inclusion, all documents referred to in this description are fully included in the present description, as well as test methods.

Table 1
Used materials Designation Description Material Beams 1 BIMS rubber, Mooney viscosity: 35 units *, 0.75 mol% Br, 5 wt.% PMS units EXXPRO ™ 89-1, ExxonMobil Chemical BIMS2 BIMS rubber, Mooney viscosity: 45 units *, 0.75 mol% Br, 5 wt.% PMS units EXXPRO ™ 89-4, ExxonMobil Chemical BIMSZ BIMS rubber, Mooney viscosity: 65 units *, 1.1 molar% Br, 5 wt.% PMS units EXXPRO ™ 91-11, ExxonMobil Chemical DM16D Tertiary amine, hexadecyldimethylamine product Armeen DM16D, Akzo Nobel Chemical DMHDT Tertiary amine, hydrogenated tall oil alkyldimethylamines ** product Armeen DMHDT, Akzo Nobel Chemical M2NT Tertiary amine, dihydrogenated tall oil alkylmethylamines product Armeen M2HT, Akzo Nobel Chemical

* Mooney viscosity was determined at 125 ° C, standard ASTM D1646.

** hydrogenated tall oil contains the following saturated products: 3.5% C ₁₄ -, 0.5% C ₁₅ -, 31% C ₁₆ -, 1% C ₁₇ -, 61% C ₀₈ - and 3% unsaturated C ₁₈ product (2/3 of the alkyl groups are in C ₁₈ )

table 2
Mooney viscosity values of low and high Mooney viscosity Shear Rate (1 / s) Viscosity * BEAMS 2 Beams viscosity 3 one hundred 1274 1468 500 378 383 1000 200 197 1500 136 133 * Determined at 220 ° C using a capillary plastometer. Values are expressed in Pa · s. Table 3
The viscosity values of BIMS 2, modified DM16D, at 220 ° C in Pa · s. Shear Rate 1 / s Beams 2 Beams with 0.1 eq. DM16D Beams with 0.25 equiv. DM16D Beams with 0.5 eq. DM16D Beams with 1.0 eq. DM16D one hundred 1274 1673 1649 3304 2910 500 378 426 426 981 916 1000 200 230 239 571 505 1500 136 152 171 416 361 Table 4
Resistance to thermal aging of BIMS 2, modified DM16D, at a shear rate of 1 s ^-1 , determined using a vibration plastometer. Temperatures were raised from 100 to 250 ° C. lowered to 100 ° C and returned to 250 ° C at a rate of 5 ° C / min Temperature (° C) Viscosity * BEAMS with 0.25 equiv. DM16D Beams viscosity with 1.0 eq. DM16D 250 (first increase) 19770 124000 200 (first increase) 21089 124000 150 (first increase) 26387 117000 100 (first increase) 39526 111,000 Temperature (° C) Viscosity * BEAMS with 0.25 equiv. DM16D Beams viscosity with 1.0 eq. DM16D 150 (second boost) 25862 111,000 200 (second boost) 21600 125000 250 (second boost) 18909 131000 * Values are expressed in Pa · s. Table 5
The viscosity values of BIMS 2 modified with DMHTD at 220 ° C in Pa · s. Shear Rate (1 / s) Beams 2 Beams with 0.1 eq. DMHTD Beams with 0.25 equiv. DMHTD Beams with 0.5 eq. DMHTD Beams with 1.0 eq. DMHTD one hundred 1274 1892 1916 3209 * 500 378 517 594 861 963 1000 200 317 315 472 499 1500 136 * 211 312 339 Table 6
The viscosity values of BIMS 2, modified M2NT, at 220 ° C in Pa · s. Shear Rate (1 / s) Beams 2 Beams with 0.1 eq. M2NT Beams with 0.25 equiv. M2NT Beams with 0.5 eq. M2NT Beams with 1.0 eq. M2NT one hundred 1274 B / I * 1997 2372 2227 500 378 B / I 496 645 679 1000 200 B / I 263 368 388 1500 136 B / I 182 276 275 * B / I means no change with respect to the pure BIMS 2 parameter

Table 7
Beam dispersion particle sizes Mixture The particle size of the dispersion (in micrometers) Control sample 2.08 Modified Beams 1.42 Table 8
A mixture of a copolymer with polypropylene Component / Property (parts by weight) Control sample (but) (b) (at) PP 4772 eighteen eighteen eighteen eighteen Beams 1 27 27 27 27 Armeen DM16D - 1,5 1,0 0.5 Oil 4,5 4,5 4,5 4,5 Irganox 1076 0.09 0.09 0.09 0.09 MgO (Maglite D) 0.135 0.135 0.135 0.135 100% elongation stress, psi 570 950 830 720 Elongation stress by 200%, psi inch - 1170 1100 960 The strain at break,% 130 500 470 410 The maximum voltage near the moment of rupture, psi 580 1800 1600 1400 Tensile Strength, psi inch 670 6240 2440 1850 Table 9
A mixture of a copolymer with polypropylene Component / Property (parts by weight) Control sample Control sample (g) (d) PP 4772 13.5 13.5 13.5 13.5 Beams 1 31.5 31.5 31.5 31.5 Component / Property (parts by weight) Control sample Control sample (g) (d) Armeen DM16D - - 1.16 1.16 Oil 4,5 9.0 4,5 9.0 Irganox 1076 0.09 0.09 0.09 0.09 MgO (Maglite D) 0.135 0.135 0.135 0.135 100% elongation stress, psi one hundred 75 440 280 200% elongation stress, psi 70 24 660 460 The strain at break,% 570 350 640 680 The maximum voltage near the moment of rupture, psi 8 3 1380 1100 Tensile Strength, psi 270 120 5470 4430 Table 10
A mixture of a copolymer with polypropylene Component / Property (parts by weight) Control sample Control sample Control sample (e) (g) (3) PP 4772 13.5 13.5 13.5 13.5 13.5 13.5 BIMS2 31.5 31.5 31.5 31.5 31.5 31.5 Armeen DM16D - - - 1.16 1.16 1.16 Oil 4,5 9.0 13.5 4,5 9.0 13.5 Irganox 1076 0.09 0.09 0.09 0.09 0.09 0.09 MgO (Maglite D) 0.135 0.135 0.135 0.135 0.135 0.135 Voltage at 100% elongation 180 130 36 550 320 440 psi Voltage at 200% elongation 160 one hundred 26 830 510 630 psi Component / Property (parts by weight) Control sample Control sample Control sample (e) (g) (3) The strain at break,% 650 920 1280 710 710 600 The maximum voltage near the moment of rupture, psi 35 3 0.2 1900 1230 1200 Tensile strength psi 730 450 110 8100 5200 4500

Claims (36)

1. Thermoplastic composition of high viscosity, comprising at least one isoolefin copolymer containing a unit derived from halomethylstyrene mixed with at least one hindered amine or phosphine compound having a corresponding structure R ₁ R ₂ R ₃ H or R ₁ R ₂ R ₃ P, where R ₁ is H or C ₁ -C ₆ alkyl, R ₂ is C ₁ -C ₃₀ alkyl, and R ₃ is C ₄ -C ₃₀ alkyl and, in addition, R ₃ is higher alkyl than R ₁ , and thermoplastic material. 2. The thermoplastic composition according to claim 1, where the isoolefin copolymer and amine or phosphine are mixed before adding the thermoplastic material, and the mixture is carried out at a temperature higher than the melting temperature of the specified obstructed amine or phosphine compounds. 3. The thermoplastic composition according to claim 1, in which the thermoplastic material is from 10 to 90 wt.% The composition. 4. The thermoplastic composition according to claim 1, wherein the thermoplastic material is selected from the group consisting of polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, polyacetals, acrylonitrile / butadiene / styrene copolymer resins, polyphenylene oxides, ethylene carbon monoxide copolymers , polyphenylene sulfides, polystyrenes, styrene / acrylonitrile copolymer resins, resins from styrene / maleic anhydride copolymers, aromatic polyketones and mixtures thereof. 5. The thermoplastic composition according to claim 1, in which vulcanizing groups are essentially absent. 6. The thermoplastic composition according to claim 1, in which R ₃ denotes alkyl With ₁₀ -C ₂₀ . 7. The thermoplastic composition according to claim 1, wherein the hindered compound is a tertiary amine, wherein R ₃ is C ₁₀ -C ₂₀ alkyl. 8. The thermoplastic composition according to claim 3, where each of R ₁ and R ₂ is methyl. 9. The thermoplastic composition according to claim 1, containing from 0.05 to 2 mol of amine or phosphine per halogen. 10. The thermoplastic composition according to claim 1, in which the isoolefin copolymer is a halogenated poly (isobutylene-co-p-methylstyrene). 11. The thermoplastic composition according to claim 7, which is a vulcanized composition having a strain at break of more than 200%, as determined by ASTM D1708. 12. The thermoplastic composition according to claim 7, which is a vulcanized composition having a tensile strength greater than 1000 psi, as determined by ASTM D1708. 13. A method of preparing a thermoplastic composition of high viscosity, comprising mixing at least one isoolefin copolymer containing a unit derived from halomethylstyrene, at least one hindered amine or phosphine compound having a corresponding structure R ₁ R ₂ R ₃ N or R ₁ R ₂ R ₃ P, where R ₁ is H or C ₁ -C ₆ alkyl, R ₂ is C ₁ -C ₃₀ alkyl, and R ₃ is C ₄ -C ₃₀ alkyl and, in addition, R ₃ is higher alkyl than R _1, and a thermoplastic material with a thermoplastic release com ozitsii. 14. The method according to item 13, in which the mixing is carried out at a temperature of from 150 to 240 ° C. 15. The method according to item 13, where the thermoplastic material is from 10 to 90 wt.% The composition. 16. The method according to item 13, where the thermoplastic material is selected from the group comprising polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, polyacetals, acrylonitrile / butadiene / styrene copolymer resins, polyphenylene oxides, ethylene-carbon monoxide sulfide copolymers, polyenes , polystyrenes, styrene / acrylonitrile copolymer resins, resins from styrene / maleic anhydride copolymers, aromatic polyketones and mixtures thereof. 17. The method according to item 13, where the thermoplastic polymer is a polypropylene or nylon. 18. The method according to item 13, where R ₃ denotes alkyl With ₁₀ -C ₂₀ . 19. The method according to item 13, where the vulcanizing group is essentially absent. 20. The method according to item 13, where each of R ₁ and R ₂ denotes methyl. 21. The method according to item 13, where the copolymer contains from 0.05 to 2 mol of amine or phosphine per halogen. 22. The method according to item 13, in which the mixing is carried out essentially in the absence of a solvent. 23. The method according to item 13, where the isoolefin copolymer is a halogenated poly (isobutylene-so-p-methylstyrene). 24. Thermoplastic composition of high viscosity, prepared according to the method according to item 13. 25. A method of preparing a thermoplastic composition of high viscosity, comprising first mixing at least one isoolefin copolymer containing a unit derived from halomethylstyrene, at least one hindered amine or phosphine compound having a corresponding structure R ₁ R ₂ R ₃ N or R ₁ R ₂ R ₃ P, where R ₁ is H or C ₁ -C ₆ alkyl, R ₂ is C ₁ -C ₃₀ alkyl, and R ₃ is C ₄ -C ₃₀ alkyl and, in addition, R ₃ is higher alkyl, than R _1, the allocation amine composition or phosphine / copolymer CME ix amine composition or phosphine / copolymer with the thermoplastic material and recovering the thermoplastic composition. 26. The method according A.25, in which the mixture is carried out at a temperature higher than the melting point of the specified obstructed amine or phosphine compounds. 27. The method according A.25, where the thermoplastic material is from 10 to 90 wt.% The composition. 28. The method according A.25, where the thermoplastic material is selected from the group consisting of polyolefins, polyamides, polyimides, polyesters, polycarbonates, polysulfones, polylactones, polyacetals, acrylonitrile / butadiene / styrene copolymer resins, polyphenylene oxides, ethylene-carbon monoxide phenol copolymers, poly , polystyrenes, styrene / acrylonitrile copolymer resins, resins from styrene / maleic anhydride copolymers, aromatic polyketones and mixtures thereof. 29. The method according A.25, where the thermoplastic polymer is a polypropylene or nylon. 30. The method according A.25, where the composition of the amine or phosphine / copolymer has a viscosity at 220 ° C and a shear rate of 100 1 / s, comprising from 1300 to 6000 PA · s, which is determined according to ASTM D1646. 31. The method according A.25, where the composition of the amine or phosphine / copolymer has a viscosity at 220 ° C and a shear rate of 1000 1 / s, exceeding 200 PA · s, which is determined according to ASTM D1646. 32. The method according A.25, in which the mixing is carried out essentially in the absence of a solvent. 33. The method according A.25, where the vulcanizing group is essentially absent. Prioritization of claims: 11.10.2000 according to claims 1, 2, 7, 9, 10, 13, 21, 23-26, related to the use of a hindered amine compound; 06/07/2001 according to claims 1, 2, 3, 6, 8, 9, 13, 15, 18, 20, 21, 24, 25-27 related to the use of hindered phosphine compounds; 10/09/2001 according to claims 4, 5, 11, 12, 14, 16, 17, 19, 22, 28-33.